Method for simultaneous extraction of essential oils and antioxidants from Labiatae species and the extract products thereof

ABSTRACT

An increase in specific antioxidant activity of extracts from rosemary ( Rosemarinus officinalis ) is obtained by the use of a blend of tetrafluoroethane and acetone in the extraction process. A blend of tetrafluoroethane, acetone and methanol improves total yield. A tetrafluoroethane and acetone blend has higher efficacy but comparatively lower yields. The methods yield a liquid and oily antioxidant extract that is readily mixed with a liquid product such as soybean oil for addition to animal feeds and human food. The methods simultaneously yield pharmaceutical grade essential oils in high yields.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates generally to a method for simultaneous extractionof essential oils and antioxidants from organic material, moreparticularly organic material from the Lamiaceae (or Labiatae) family,including rosemary (Rosemarinus officinalis) and, more specifically, toa method of simultaneous extraction of essential oils and antioxidantsfrom species of the family Labiatae, in particular, rosemary, usingsolvent blends and which yields a liquid, oily extract containingantioxidants and a liquid extract containing essential oils. The extractcontaining antioxidants is readily mixed with an edible oil for additionto animal feeds and human food. The essential oils are pharmaceuticalgrade.

2. Background of the Prior Art

Worldwide demand for natural antioxidants has been rising due to safetyconcerns about synthetic food and feed additives and the publicperception that natural food and feed supplements provide certain healthbenefits. The most important natural antioxidants being exploitedcommercially today are tocopherols. Tocopherols have a potent ability toinhibit lipid peroxidation in vivo by trapping peroxy-radicals (Burton,G. W., and K. U. Ingold (1989), in Vitamin E: Biochemistry and HealthImplications, edited by A. T. Diplock, L. J. Machlin, L. Packer and W.A. Pryor, The New York Academy of Sciences, New York, pp. 7-22). Variousherbal extracts for use as natural antioxidants are being explored.Possibilities include the extraction of rosemary or other botanicalsources. Such new antioxidants may play a role in combatingcarcinogenesis as well as the aging process, and may be applicable inthe nutraceutical industry.

Among the various natural extracts available in the market are rosemaryextracts, which are reported to be highly effective in retarding lipidoxidation and protecting living cells from the damaging oxidative stress(Chen, Q., H. Shi and C-T Ho (1992), “Effects of rosemary extracts andmajor constituents on lipid oxidation and soybean lipoxygenaseactivity”, J Am Oil Chem Soc 69: 999-1002; Wong, J. W., K. Hashimoto andT. Shibamoto (1995), “Antioxidant activities of rosemary and sageextracts and vitamin E in a model meat system”, J Agric Food Chem 43:2707-2712). These extracts are described as being superior to vitamin E,a well-known natural antioxidant and food supplement, in many food modelsystems (Lolinge, J. (1983), Natural antioxidants in Allen, J. C. and R.J. Hamilton eds, Rancidity in Foods, Elsevier Applied Science, London,Chapter 6). However, opposite findings are also documented. Wong et al.(1995) revealed that vitamin E is more effective than rosemary extractin a cooked beef homogenate. Additionally, rosemary extract is shown tobe a synergist of vitamin E in stabilizing or retarding oxidation insardine oil and fish muscle (Fang, X. and S. Wanda (1993), “Enhancingthe antioxidant effect of α-tocopherol with rosemary extract ininhibiting catalyzed oxidation caused by Fe²⁻ and hemoprotein”, Food ResInt 26: 405-411; Wanda, S. and X. Fang (1992), “The synergisticantioxidant effect of rosemary extract and α-tocopherol in sardine oilmodel system and frozen-crushed fish meat”, J Food Process Preserv 16:263-274).

As to the extraction of rosemary, many authors report that polarsolvents yield extracts with higher antioxidant activities (Chang, S.S., B. Ostric-Matijasevic, C-L Huang and OA-L Hsieh (1977), “Naturalantioxidants from rosemary and sage”, J Food Sci 42: 1102-1106). Chen etal. (1992) found that hexane extracts of rosemary contained a highercontent of carnosic acid and carnosol than methanol extracts do.Carnosic acid and carnosol are the effective antioxidant molecules inrosemary. Carnosic acid and carnosol have been suggested to account forover 90% of the antioxidant activity of rosemary extracts (Aruoma, O. I,B. Halliwell, R. Aeschbach and J. Loligers (1992) “Antioxidant andpro-oxidant properties of active rosemary constituents: carnosol andcarnosic acid”, Xenobiotica 22: 257-268). Antioxidant molecules ingeneral, and rosemary antioxidants specifically, are by nature labilemolecules especially when exposed to heat and/or air. During theharvest, the drying, and the regular solvent extraction of rosemary,some oxidation is likely to occur. Through a process of chemicalreactions, carnosic acid, the naturally-occurring antioxidant moleculein rosemary, is believed to be the precursor to carnosol and many otherantioxidants found therein (Wenkert, E., A. Fuchs, J. D. McChesney(1965), “Chemical artifacts from the family labiate”, J. Org. Chem. 30:2931-2934). It can be demonstrated that the freshly cut leaves ofrosemary do not contain carnosol (Aeschbach, R. and L. Philippossian(1993), “Carnosic acid obtention and uses”, U.S. Pat. No. 5,256,700).Carnosic acid is about 10 times more effective as an antioxidant thancarnosol (Aruoma et al., 1992), and it, therefore, is important for thehigh activity of a rosemary extract to minimize the damage to carnosicacid.

Essential oils are volatile oils which are the aroma and flavorcomponents of organic material. They are used in a variety of productssuch as incense, aromatherapy oils, perfumes, cosmetics,pharmaceuticals, beverages, and foods. The market for these oils demandsconsistent high quality and reliable supplies at competitive prices.Essential oils are typically commercially extracted from organicmaterial such as rosemary using steam distillation. In this prior artprocess, the antioxidants are destroyed, and thermal degeneration of theessential oils may occur.

The antioxidant activity of commercially available rosemary products wascompared with rosemary extracts prepared in the laboratory using varioussolvents for extraction. It was found that the antioxidant activity ofcommercial rosemary products was in the range of 2-5% when compared tomixed tocopherols. A methanol extract had 10% of the activity of mixedtocopherols. Methanol extraction, moreover, results in a dry powder thatis difficult to dissolve into preferred carriers, such as edible oils.Accordingly, there were identified goals to increase the specificactivity of extracts of species of the family Labiatae, includingrosemary, by optimizing the solvent extraction methodology, to testalternate extraction technologies, and to improve the handlingcharacteristics of the extract.

The investigation into alternate extraction technology had two primaryobjectives. Firstly, to increase the specific activity of the rosemaryextracts further for more efficient formulation into soybean oil orother carrier; and, secondly, to identify technology allowing theremoval of the essential oil fraction from the extracted materialwithout oxidative destruction of the carnosic acid. One extractiontechnique investigated is based on tetrafluoroethane (TFE).

A process for the extraction of antioxidants and essential oils fromrosemary preferably meets several criteria. It should be economical andalso lead to a liquid or oil antioxidant extract that can be formulatedinto a homogeneous, soybean oil-based final product that is largely freeof odor.

For the foregoing reasons, it is desired that a process be found thatsimultaneously yields antioxidants and essential oils suitable forfurther commercial use via a single solvent mix. The present inventionsolves this problem with sufficiently high yields and purities to be acommercially-viable process.

SUMMARY OF THE INVENTION

This invention is directed to a method of simultaneously extractingantioxidants and essential oils from organic materials and the extractproducts of the method.

A purpose of the invention is to identify a solvent blend and extractionparameters for the extraction of antioxidants of rosemary whileattaining a high specific activity and retaining high extraction yields.

Another purpose of the present invention is to provide a method forextracting antioxidants from rosemary that yields a liquid, oily extractthat is readily mixed with a liquid product, such as soybean oil, forincorporation into animal feeds and human foods.

A further purpose of the present invention is to provide a method forextracting essential oils from rosemary in high yields and high purity.

The organic material used during testing was dried, finely groundrosemary of the Arp variety. It is anticipated that the organic materialcan be any plant of the Labiatae family, and more broadly, any plantmaterial which contains antioxidants and essential oils. It is alsoexpected that any parts of the plant which contain the desiredcomponents may be extracted, as well as any form of the plant material(e.g., whole, ground, fresh, or dried).

Tetrafluoroethane was used in the solvent blend. Tetrafluoroethane has aboiling point of −27° C. The technology utilizes the vapor pressure ofthe solvent at room temperature and allows extraction under mildconditions, therefore minimizing the oxidative decomposition of carnosicacid during the extraction process. Tetrafluoroethane is substantiallyapolar and is preferably blended with acetone in the extractions ofrosemary described here. The advantages of TFE show that it isnon-flammable, has a low boiling point, is environmentally acceptable(very low toxicity), and is easily handled. It has been found that atambient or sub-ambient temperatures, TFE leaves behind the majority ofthe waxes and other non-fragrant materials normally extracted withconventional solvents (Wilde P. F., 1994. Fragrance Extraction. EuropeanPatent No. 0616821A1). Another advantage with the use of TFE is that nodistillation must be employed due to its low boiling point. It isanticipated that any hydrofluorocarbon (HFC) with a hydrocarbon backboneof three carbons or fewer (C1-C3) may be used, or mixtures thereof.Acetone and methanol were the organic solvents in the solvent blend.Though methanol alone extracts the antioxidants from rosemary veryeffectively, it leads to a dry powder extract and an inferior liquidfinal product after formulation into soybean oil. The optimum TFE-basedsolvent blend for the extraction of antioxidants from rosemary wasidentified and extraction parameters were defined. Among numeroussolvent blends tested, an 80/15/5 weight percent blend ofTFE/methanol/acetone, respectively, proved to be the most effectivesolvent resulting in a liquid extract with up to 35% of the tocopherolefficacy and an antioxidant yield of about 60% of the rosemaryantioxidants. Mixtures of TFE and hexane or butane have been tested aswell. Though hexane or butane works, they are not as efficient asacetone and methanol. It is anticipated that similar individual organicsolvents added to the TFE may be used as well, or mixtures thereof.Examples include, but are not limited to, ethanol, ethylene chloride,isopropanol, methylene chloride, propylene glycol, and other food gradesolvents. Yields may differ with different solvent mixtures, but anysimilar solvent mixture should simultaneously yield essential oils andantioxidants using the present process.

The organic material and solvent blend are added together in a 1:3(organic material:solvent blend) or higher (i.e., 1:4, 1:5, etc.) weightratio to perform the extraction step in any vessel which will becompatible with the components. Since the TFE is preferably added inliquid form, the vessel has to be a pressure vessel which will withstandpressures equal to those required to maintain the TFE in liquid form.The extraction has been carried out at ambient temperatures, but thepressure and temperature may be varied, so long as the TFE and organicsolvents remain in liquid form. The extraction appears to be almostinstantaneous when dried, finely ground rosemary is used, as there wasno appreciable difference in efficacy of products and only smalldifferences in yield whether the extraction is done for 5 minutes or 2hours. The extraction has been carried out at greater than ambienttemperature (up to approximately 40° C.) and found to increase yields(e.g., 7-8% crude extract at standard temperature and pressure and 17%crude extract at 40° C.) with a decline in efficacy of the products anda change in the physical characteristics of the final product due towhat is believed to be an increased extraction of longer chainhydrocarbons.

The method for removing the organic material from the solution wasfiltration. Any suitable separation process known to one skilled in theart which does not interfere with the other steps of the method may beused.

The removal of the solvent blend has been accomplished by evaporation.Specifically, the removal has been in steps in order to remove thesolvents selectively. The TFE may be removed by any suitable methodknown to one skilled in the art. A thin film evaporator is anticipatedto be suitable for this process. The organic solvent(s) may be removedby any suitable method known to one skilled in the art as well. A wipefilm evaporator is anticipated to be suitable for this process.

Once the TFE is removed, it may be cooled or the pressure increaseduntil it reaches its liquid phase and recycled back for reuse. Removalof the organic solvent(s) in the wipe film evaporator yields the oily,liquid antioxidants. The organic solvent(s) may be further treated byany suitable process known to one skilled in the art, specificallycolumn distillation, to separate the organic solvent(s) from theessential oils. The resulting essential oils are of very high purity(pharmaceutical grade) and surprisingly high yields (compared toprevious extraction methods for obtaining essential oils).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process diagram of the preferred embodiment of theextraction method of the present invention.

FIG. 2 is a chart of the antioxidant efficacy of a number of samples ofrosemary extracted according to described Method 1.

FIG. 3 is a chart of the antioxidant efficacy of a number of samples ofrosemary extracted according to described Method 1.

FIG. 4 is a chart of the antioxidant efficacy of a number of samples ofrosemary extracted according to described Method 1.

FIG. 5 is a chart of the antioxidant efficacy of a number of samples ofrosemary extracted according to described Method 1.

FIG. 6 is a chart of the antioxidant efficacy of a number of samples ofrosemary extracted according to described Method 1.

FIG. 7 is a chart of the antioxidant efficacy of a number of samples ofrosemary extracted according to described Method 2.

FIG. 8 is a chart of the antioxidant efficacy of a number of samples ofrosemary extracted according to described Method 3.

FIG. 9 is a chart of the antioxidant efficacy of a number of samples ofrosemary extracted according to described Method 4.

FIG. 10 is a schematic diagram of extraction Method 1 of the presentinvention.

FIG. 11 is a schematic diagram of extraction Method 2 of the presentinvention.

FIG. 12 is a schematic diagram of extraction Method 3 of the presentinvention.

FIG. 13 is a schematic diagram of extraction Method 4 of the presentinvention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The preferred embodiment of the method of the present invention is shownin FIG. 1. The process includes an extraction vessel 10 where theorganic material 12 is extracted using the solvent blend at a pressureequal to that necessary to keep the TFE in liquid form and at ambienttemperature. The solvent blend is premixed in a solvent blend tank 14before being added to the extraction vessel 10 where the organicmaterial 12 has been added. The solvents are added to the solvent blendtank 14 from fresh supply tanks, acetone tank 16, methanol tank 18, andTFE tank 20, or alternatively, recycled from the end separationtechniques.

After the desired natural organic components are extracted from theorganic material 12 after a sufficient residence time, the mixture ispassed through a filter 22. The filtered extract then passes through athin film evaporator 24 where the TFE is removed and the remainingextract passes to the next step. The removed TFE is recycled backthrough a cold-trap 26 to the TFE tank 20 for reuse.

The TFE-free extract then passes through a wipe film evaporator 28 wherethe liquid, oily antioxidant portion of the extract 30 is collected andthe organic solvent portion of the extract is treated further. Theorganic solvent portion of the extract passes through columndistillation 32 to separate the essential oils 34 from the organicsolvents. The organic solvents are condensed in a cold-trap 26 beforebeing recycled back to the solvent blend tank 14.

The methods of this invention are further illustrated by the followingexperimental examples.

EXAMPLES Example 1

The invention identifies methods of extracting rosemary with differentTFE-based solvents and define preferred extraction conditions. A totalof 17 different solvent blends, individually and combined, were used.Data presents the results of the analysis of extracts of rosemaryproduced from the Arp variety in terms of extraction yield (%) andpercent efficacy when compared to 100% mixed tocopherols at equalapplications of 500 ppm tested in chicken fat, and rosemaryextract/tocopherols equivalency.

All samples were tested in untreated chicken fat at a treatment level of500 ppm. These samples were then placed into an oxygen bomb pressurizedto 50 psi with oxygen, placed in silicon oil at 100° C. and allowed tooxidize. All samples were compared against the induction time of fattreated with 250 ppm 100% mixed tocopherols at a calculated equalconcentration level of 500 ppm.

In the data tables, the sample number, the solvent used, percent yield,percent efficacy of tocopherols, and equivalency of rosemary extract tograms of tocopherols are reported. The percent yield was calculated bydividing the yield of rosemary extract by the initial mass of rosemaryand multiplication by 100%. The percent efficacy to tocopherols wascalculated as follows:$\frac{{{IT}_{sample}\left( {500\quad{ppm}} \right)} - {IT}_{control}}{2\left( {{IT}_{{tocopherols250}\quad{ppm}} - {IT}_{control}} \right)} \times 100\quad\%$

-   -   where “IT” is the induction time.

Tocopherol equivalent units (g) were calculated using the assumptionsthat 1.0 kg rosemary was extracted according to the individual methods,and the percent yield and percent efficacy are equivalent from the smallscale to the large scale extraction process:1000 g rosemary×(% yield/100%)×(% efficacy/100%)=tocopherol equivalent(g).

The poultry fat, used as a test matrix, was supplied from Tyson. Thevarious rosemary accessions were obtained from the Chart Co., PapaGeno's Herb Garden, and the North Carolina Botanical Garden. Allsolvents were purchased from Fisher Scientific Co. The apparatus thatthe TFE/organic experiments were conducted in was purchased from theAdvanced Phytonics facility in Cowfold Grange, Leeming, U.K. Allrosemary leaves used in these experiments were from the Arp varietyunless otherwise noted.

Method 1 Effect of Solvent Blends on Efficacy

For samples 1-17, 2.0 g of dried, ground rosemary leaves were introducedinto a closed glass vial extractor. The sample was then extracted with20 g tetrafluoroethane (TFE) or a TFE/solvent mix for two hours. At thistime the filtrate was quantitatively transferred into a glass collectionvial. The rosemary was then washed with 10.0 g of the extractionsolution for five minutes. This liquid portion was added to the firstfiltrate collected. The rosemary was washed a second time with 10.0 g ofthe extracting solution and this was also added to the collection vial.After all of the filtrate solutions had been combined, the pressure inthe vial was slowly released. After all of the TFE had evaporated, theother organic solution was removed under a stream of nitrogen gas undermoderate heating. The extraction process is illustrated diagrammaticallyin FIG. 10.

The purpose of this series of experiments (FIG. 2, samples 1-7) was totest the performance of various TFE/acetone blends for the extraction ofantioxidants from rosemary. When used alone, TFE results in poor yieldwith low efficacy. Acetone was added in small amounts to the TFE,initially at a concentration of 5%. The efficacy of the extracts wasincreased dramatically, up to six-fold, when sample number 2 (95% TFE/5%acetone) was compared to the efficacy of the sample number 1 (100% TFE).As the concentration of the acetone was increased, yields increasedsteadily while the specific efficacy remained essentially the same afteran initial steep increase. It appears that with increasingconcentrations of acetone, the blend equally well extracts antioxidantcomponents as well as non-antioxidant components. The yield data arepresented in Table 1 and the antioxidant efficacy is illustrated in FIG.2.

TABLE 1 Tocopherol % Efficacy Equivalent No. Solvent % Yield toTocopherols Units (g) 1 100% TFE 0.95  5.84 0.555 2  95% TFE/5% acetone3.27 35.71 11.7 3  90% TFE/10% acetone 5.06 37.01 18.7 4  85% TFE/15%acetone 6.50 35.71 23.21 5  80% TFE/20% acetone 6.11 34.41 21.0 6  75%TFE/25% acetone 6.54 34.41 22.5 7  70% TFE/30% acetone 7.49 27.92 20.9

The purpose of the next set of experiments (FIG. 3, samples 1, 8-13) wasto test the effect of varying the concentration of hexane when mixedwith TFE. Generally, the effect of hexane added to TFE had a lesspronounced effect on the performance when compared to the acetoneresults. However, as was observed with the acetone, hexane was also ableto improve the efficacy of the extracts by five-fold when compared tosample number 1 (100% TFE). The yield data are presented in Table 2 andthe antioxidant efficacy is illustrated in FIG. 3.

TABLE 2 Tocopherol % Efficacy Equivalent No. Solvent % Yield toTocopherols Units (g)  1 100% TFE 0.95  5.84 0.555  8  95% TFE/5% hexane1.90 24.02 4.6  9  90% TFE/10% hexane 2.79 24.02 6.7 10  85% TFE/15%hexane 4.85 24.02 11.6 11  80% TFE/20% hexane 5.69 24.02 13.7 12  75%TFE/25% hexane 5.46 26.62 14.53 13  70% TFE/30% hexane 6.40 26.62 17.0

FIGS. 4 and 5 (samples 2-13) compare the two different groups of solventsystems in terms of yields and specific activity. A steady increase inextraction yields can be noted as the TFE is replaced by the twosolvents hexane or acetone. As to the specific activity, a rapidincrease followed by a long plateau is observed. On average theTFE/acetone extracts outperformed the TFE/hexane extracts by about 10%in terms of specific activity. However, at a concentration of 30% forboth solvents, the extracts were approximately equal in efficacy.

Additional solvents and solvent mixes were tested in an attempt toincrease the efficacy and the total antioxidant yield extracted from therosemary. Table 5 and FIG. 6 (samples 1 and 14-17) display the resultsof these experiments. When a 90% TFE/10% butane blend was evaluated athree-fold increase in efficacy over sample number 1 (100% TFE) wasobserved. The TFE/butane extract was equal to a methanol extract. Next,several three-solvent blends were tested. The two solvents mixed withTFE were methanol and acetone, varying in concentration from 5 to 15percent (see Table 4). Using a solvent mix of 80% TFE/15% MeOH/5%acetone, the extract obtained displayed the highest total yield with aspecific efficacy of 29.22% of that of tocopherol and an extractionyield of 10.05%. Methanol in combination with acetone seems to augmentextraction yields while maintaining high specific efficacy. The yielddata are presented in Table 3 and the antioxidant efficacy isillustrated in FIG. 6.

TABLE 3 Tocopherol % Efficacy Equivalent No. Solvent % Yield toTocopherols Units (g)  1 100% TFE 0.95  5.84 0.555 14  90% TFE/10%butane NA 20.12 — 15  80% TFE/5% MeOH/ 7.85 30.52 23.9  15% acetone 16 80% TFE/10% MeOH/ 6.34 34.42 21.8  10% acetone 17  80% TFE/15% MeOH/10.05  29.22 29.4  5% acetone

Method 2 Effect of Multiple Extractions on Efficacy and Yield

For sample 18, 2.0 g of dried ground rosemary leaves were introducedinto the glass-extracting vial. The sample was then extracted with 20.0g of 85% TFE/15% acetone for two hours. This was repeated once more. Atthis time 40.0 g of the solvent mix was added to the extraction vialcontaining the rosemary. This was allowed to stand for 20 hours. Thesolvent was then removed and added to the previous two extracts. The TFEwas then allowed to evaporate off and the acetone was removed under astream of nitrogen gas with slight heat. The process is illustrateddiagrammatically in FIG. 11.

The possibility of attaining higher yields with repeated extractionswhile retaining the high efficacy of the extracts was explored. FIG. 7represents the antioxidant activity of sample 18. Sample 18 was producedfrom the repeated extraction of rosemary over a 24-hour period using 85%TFE/15% acetone. No appreciable increase in the yield or decrease inefficacy was observed when compared to a single extraction. Table 4presents the yield data.

TABLE 4 Tocopherol % Efficacy Equivalent No. Solvent % Yield toTocopherols Units (g) 18 85% TFE/15% acetone 6.70 33.12 22.2

Method 3 Effect of Extracting a Methanol Extract of Rosemary with a TFEBlend

Sample 19 was prepared by taking 100.0 g of Arp rosemary leaves andextracting it with 600 ml of methanol for 48 hours. This was thenfiltered and the methanol was evaporated via vacuum rotary evaporator at40° C. Samples 20 and 22 were prepared by taking 1.0 g of sample 19 andputting it into a glass-extracting vial. For sample 20, 10 g of 85%TFE/15% acetone was added to the 1.0 g of sample 19. This solution wasallowed to extract the 1.0 g sample for two hours. This solution wasthen filtered away from the sample. This was repeated once more. Bothsolutions were then combined, the TFE was allowed to boil off, and theacetone was removed under a stream of nitrogen gas with slight heat. Forsample 22, the same method was followed to prepare sample 20, however,instead of using 85% TFE/15% acetone as the extracting solvent, 70%TFE/30% hexane was used. The material (bagasse) that was left over fromthe process of preparing samples 20 and 22 was labeled 21 and 23,respectively. This process is illustrated schematically in FIG. 12.

The possibility of utilizing the TFE based extraction process to furtherdeodorize and purify a methanol extract of rosemary was explored (seeFIG. 8). Methanol extracts possess close to 100% of the antioxidantsfrom rosemary. With this in mind, TFE mixed with an organic solvent(acetone or hexane) may separate out or extract a larger majority of theantioxidants from a methanol extract over dried, ground rosemary leaves.The test was performed with both, acetone and hexane. Initial testsindicated that the TFE blend solvent extracts were approximately equalto the methanol extracts of dried, ground rosemary. The non-extractedportion, the bagasse, left over from the TFE based extraction (samples21 and 23), retained a large amount of the antioxidant activity whichhad 13.64% and 12.34%, respectively, of the tocopherol activity. Thisresidual efficacy indicated the lack of ability of the TFE/organicsolvent mix to extract 100% of the antioxidants from a methanol extractof rosemary. Table 5 presents the yield data and FIG. 8 displays theantioxidant efficacy.

TABLE 5 Tocopherol % Efficacy Equivalent No. Solvent % Yield toTocopherols Units (g) 19 100% methanol 27.66 20.13 36.0 20  85% TFE/15%acetone  3.91 38.31 15.0 21 Residue NA 13.64 — 22  70% TFE/30% hexane 6.06 33.12 20.1 23 Residue NA 12.34 —

Method 4 Extraction of Rosemary with 90% TFE/10% Acetone followed byExtraction of the Bagasse with Methanol

Sample 24 was prepared by taking 15.0 g of ground rosemary and placingit into a 250 ml-extracting vial. To this was added 100.0 g of a 90%TFE/10% acetone solvent mixture. This was allowed to stand for two hoursand then the solvent was filtered away. The TFE was allowed to boil awayand the acetone was removed under a stream of nitrogen gas with slightheat. The remaining bagasse was used to create sample 25. Sample 25 wasprepared in the following way. Firstly, the remaining unextractedrosemary left over from the preparation of sample 24 was put into a 250ml flask and 60 ml of methanol was added. This was allowed to extractfor 48 hours. At this point, the solution was filtered and the methanolwas removed via vacuum rotary evaporator at 40° C. This process isillustrated diagrammatically in FIG. 13.

Whether any residual antioxidants are left after an extraction with aTFE blend was investigated (see FIG. 9). A sample of rosemary wasextracted with a 90% TFE/10% acetone (sample 24) mix and the residualrosemary material was extracted with methanol (sample 25). The resultsindicated that a blend of TFE/10% acetone extracted approximately 30% ofthe antioxidants in rosemary. It appears that the presence of methanolin the solvent blend for the extraction of rosemary is critical foreconomical yields. The yield data are presented in Table 6 and theantioxidant efficacy displayed in FIG. 9.

TABLE 6 Tocopherol % Efficacy Equivalent No. Solvent % Yield toTocopherols Units (g) 24  90% TFE/10% acetone 4.00 31.82 12.7  25 100%methanol 23.7 12.34 29.24

Example 2 Essential Oils Analysis

A sample of 1.8 kg of dried, finely ground rosemary was extracted for 1hour at a temperature of 25-26° C. at a pressure of 7 bar using 18 kg ofa solvent blend of 80% TFE, 12% methanol, and 8% acetone. After removalof the TFE, the extract was subjected to distillation to pull off theacetone and methanol. Analysis of the distillate by gas chromatographyfollowed by mass spectroscopy showed the presence of the essential oilsα-pinene, camphene, β-pinene, β-myrcene, eucalyptol, camphor, andcaryophyllene.

Although the invention has been described with respect to a preferredembodiment thereof, it is to be also understood that it is not to be solimited since changes and modifications can be made therein which arewithin the full intended scope of this invention as defined by theappended claims.

1. A process for simultaneously extracting at least a first and a secondorganic component from botanical material, comprising the steps of: (a)selecting the botanical material from a plant of the group consisting ofrosemary, sage, hyssop, oregano, thyme, basil, marjoram, spearmint,dittany, and lavender; (b) contacting the botanical material in a vesselwith a solvent blend of tetrafluoroethane and acetone to dissolve theorganic components in the solvent blend; (c) removing the remainingbotanical material from the solution of the organic components and thesolvent blend; (d) removing the tetrafluoroethane leaving at least thefirst organic component in the acetone phase; and (e) removing thesolvent blend to isolate a liquid, oily product containing the firstorganic component having antioxidant properties from the second organiccomponent.
 2. The process of claim 1, further comprising at least oneco-solvent selected from the group consisting of ethanol, ethylenechloride, isopropanol, methanol, methylene chloride, and propyleneglycol.
 3. The process of claim 1, wherein the solvent blend comprisesfrom between about 60% to about 95% tetrafluoroethane.
 4. A process forsimultaneously extracting at least a first and a second organiccomponent from botanical material, comprising the steps of: (a)selecting the botanical material from a plant of the group consisting ofrosemary, sage, hyssop, oregano, thyme, basil, marjoram, spearmint,dittany, and lavender; (b) contacting the botanical material in a vesselwith a solvent blend of tetrafluoroethane and ethanol to dissolve theorganic components in the solvent blend; (c) removing the remainingbotanical material from the solution of the organic components and thesolvent blend; (d) removing the tetrafluoroethane leaving at least thefirst organic component in the ethanol phase; and (e) removing thesolvent blend to isolate a liquid, oily product containing the firstorganic component having antioxidant properties from the second organiccomponent.
 5. The process of claim 4, further comprising at least oneco-solvent selected from the group consisting of acetone, ethylenechloride, isopropanol, methanol, methylene chloride, and propyleneglycol.
 6. The process of claim 4, wherein the solvent blend comprisesfrom between about 60% to about 95% tetrafluoroethane.
 7. A process forsimultaneously extracting at least a first and a second organiccomponent from botanical material, comprising the steps of: (a)selecting the botanical material from a plant of the group consisting ofrosemary, sage, hyssop, oregano, thyme, basil, marjoram, spearmint,dittany, and lavender; (b) contacting the botanical material in a vesselwith a solvent blend of tetrafluoroethane and methanol to dissolve theorganic components in the solvent blend; (c) removing the remainingbotanical material from the solution of the organic components and thesolvent blend; (d) removing the tetrafluoroethane leaving at least thefirst organic component in the methanol phase; and (e) removing thesolvent blend to isolate a liquid, oily product containing the firstorganic component having antioxidant properties from the second organiccomponent.
 8. The process of claim 7, further comprising at least oneco-solvent selected from the group consisting of acetone, ethanol,ethylene chloride, isopropanol, methylene chloride, and propyleneglycol.
 9. The process of claim 7, wherein the solvent blend comprisesfrom between about 60% to about 95% tetrafluoroethane.